Method of reducing the impurity level in aqueous monomer solutions

Abstract: The present invention provides a method of reducing the impurity level, e.g. the carbonyl-compound impurity level, in aqueous monomer solutions by subjecting the aqueous monomer solutions to ultraviolet radiation.

Description: The present invention is concerned with a method of reducing the impurity level in aqueous monomer solutions and, preferably, with a method of reducing the level of carbonyl-compound impurity in aqueous monomer solutions where one or more carbonyl-compounds are present as impurity. In the production of certain monomers, ethylenically unsaturated hydrocarbons are oxidized, usually in the presence of a suitable catalyst to form the desired monomer. For example, one method for producing acrylic acid is by vapor-phase oxidation of propylene or acrolein in the presence of a catalyst. Similarly, methacrylic acid can be produced by vapor-phase oxidation of isobutylene, tert-butyl alcohol, tertiary-butyl methyl ether, methacrolein or isobutyraldehyde. The products which result from these processes are aqueous solutions of monomer which are contaminated with undesirable by-products. The aqueous monomer solutions are then extracted with a suitable solvent to recover the monomer. The organic phase containing the monomer is then stripped of the solvent in a solvent-separation step to obtain the monomer product. The low-boiling impurities are then distilled from the monomer product. Finally, the monomer product is distilled to separate high-boiling impurities. Impurities in the monomer product may, for example, include carbonyl-compounds such as acrolein, methacrolein, acetaldehyde, furfural, protoanemonin, formaldehyde, crotonaldehyde, acetone and/or benzaldehyde. These by-products, or impurities, can impart color to the product or can act as polymerization inhibitors. Additional processing steps are required to reduce or remove these impurities, thereby increasing the cost of manufacturing pure monomer products. Three general approaches have emerged for reducing the level of carbonyl-compounds in aqueous monomer systems: treating the aqueous monomer solution resulting from the vapor-phase oxidation, treating the extracted monomer/solvent mixture, and treating the glacial monomer. Generally, the treatments involve one or more distillations or the addition of one or more selectively reactive chemical agents. A representative method of reducing by-products by treating an aqueous monomer solution is described in Japanese patent 62-045219. The method disclosed therein requires treating an aqueous acrylic acid solution with bisulfite, such as an alkali metal bisulfite or ammonium bisulfite before performing the extraction. Japanese patent 62-045219 discloses that this method is effective for reducing the levels of certain low-boiling impurities, including some carbonyl-containing compounds, present in the aqueous acrylic acid solution. A representative method of reducing by-products by treating an extracted monomer/solvent mixture, is described in EP-A- 0 102 642. The method disclosed therein requires treating an extracted methacrylic acid/solvent mixture with an aqueous bisulfite solution, such as an alkali metal bisulfite or ammonium bisulfite, followed by a separation step. Japanese patent application 61-218556 discloses a method of treating either an extracted acrylic acid/solvent mixture or a glacial acrylic acid to lower the levels of impurities. Japanese patent 64-004505 discloses a method of treating either an extracted methacrylic acid/solvent mixture or a glacial methacrylic acid to lower the levels of impurities. These references disclose that after the addition of bisulfite which is introduced into the aqueous monomer solution, the addition of hydrazine compounds to the extracted monomer/solvent mixture or to the glacial monomer, further reduces the levels of low-boiling impurities, including some carbonyl-containing compounds, present in the monomer product. Japanese patent 81-41614 discloses a method of reducing the level of protoanemonin in acrylic acid by treating either the aqueous acrylic acid solution resulting from the vapor-phase oxidation, the extracted acrylic acid/solvent mixture, or the glacial acrylic acid. The method disclosed therein requires the addition of 0.5% to 1% by weight of the solution to which it is being added of a nitrous acid salt, nitrogen oxide or nitrosobenzene, and a polymerization inhibitor. US-A- 3,725,208 is directed to a method of treating glacial acrylic acid to reduce the levels of aldehyde impurities. This patent discloses that the addition of sulfuric acid, hydrazine, phenylhydrazine, aniline, monoethanolamine, ethylenediamine or glycine to glacial acrylic acid followed by a distillation results in a reduction in the level of aldehyde impurities in the acrylic acid. US-A- 3,893,895 is directed to a method of treating glacial 1,2-unsaturated carboxylic acids to reduce the level of carbonyl compounds which are present as impurities. The carbonyl compounds include acrolein, formaldehyde, methacrolein, crotonaldehyde, acetaldehyde, acetone and furfural. According to the disclosure of US-A- 3,893,895, the levels of these compounds in the 1,2-unsaturated carboxylic acids are reduced by treating the glacial acid with an amine and distilling the mixture. The amines which are disclosed as being useful are inorganic amines, primary and secondary aliphatic and aromatic amines, such as hydrazine, hydroxylamine, 1,2-ethanolamine, 1,2-ethylenediamine, octyl amine, 1,3-propanolamine, 1,2-propanolamine, octadecyl amine, aniline, p-phenylenediamine, o-phenylenediamine, 1,2-dianilinoethane, alpha naphthyl amine, beta naphthyl amine, p-methyl aniline, o-methyl aniline, N-methyl aniline, semi-carbazide, phenyl hydrazine, and 2,4-dimethyl aniline. The methods of the prior art require the use of chemical additives as a means for reducing the level of impurity present therein. This approach may increase the cost and complexity of the purification process, may result in contaminating the product with other impurity, and may necessitate further purification steps. The present invention seeks to overcome the problems of the prior art. According to the present invention, there is provided a method of reducing the impurity level in an aqueous monomer solution, which comprises subjecting the aqueous monomer solution, containing the impurity, to ultraviolet radiation for from 2 minutes to 5 hours. The method of the present invention is preferably used to reduce the level of carbonyl-compound impurity. Carbonyl-compound impurity, which may be present in aqueous monomer solutions, includes, for example, carbonyl-compound impurity selected from acrolein, methacrolein, acetaldehyde, furfural, protoanemonin, formaldehyde, crotonaldehyde, acetone and benzaldehyde. Preferably, the method of the present invention is used to reduce the level of carbonyl-compound impurity wherein such impurity is selected from furfural, protoanemonin and benzaldehyde. The aqueous monomer solutions are, preferably, aqueous solutions of acrylic acid or methacrylic acid. The aqueous monomer solutions may range from about 10 percent by weight to about 95 percent by weight monomer. Preferably, the aqueous monomer solution is from about 15 percent by weight to about 90 percent by weight monomer, and most preferably from about 20 percent to about 65 percent by weight monomer. As the monomer concentration increases, there is an increased risk of undesirable polymer formation when the monomer solution is exposed to ultraviolet radiation. In one embodiment of the present invention, the impurity level, e.g. the carbonyl-compound impurity level, is reduced by at least 5% by weight based on the amount of impurity in the original impurity-containing monomer solution. The impurity level in aqueous monomer solutions is reduced by subjecting the aqueous monomer solution containing the impurity to ultraviolet radiation for from 2 minutes to 5 hours, and preferably for from 5 minutes to 3 hours. The ultraviolet radiation may be produced by any suitable source such as, for example, a mercury vapor lamp. Suitable means for subjecting the aqueous monomer solution containing the impurity, e.g. carbonyl impurity, to ultraviolet radiation include a stationary or stirred sample of aqueous monomer solution in the presence of an ultraviolet light source, and passing or recirculating a stream of the aqueous monomer solution through one or more regions where the stream will be exposed to an ultraviolet light source. Preferably, the aqueous monomer solution containing the impurity, e.g. carbonyl impurity, is subjected to ultraviolet light by passing or recirculating a stream of the aqueous monomer solution through one or more regions where the stream will be exposed to an ultraviolet light source. The aqueous monomer solution is subjected to ultraviolet radiation for from 2 minutes to 5 hours, which can be a single continuous exposure or two or more intermittent exposures providing a total average time of exposure of from 5 minutes to 5 hours, preferably from 15 minutes to 3 hours. It is known that ultraviolet radiation can initiate polymerization of ethylenically unsaturated monomers. Therefore, it is preferred that the aqueous monomer solution, containing the impurity, is inhibited with one or more polymerization inhibiting compounds. Polymerization inhibiting compounds are well known to those skilled in the art and include, for example, hydroquinone ("HQ"), hydroquinone monomethyl ether, hydroquinone monoethyl ether, benzoquinone, phenothiazine, and alkylphenols. Preferably, polymerization inhibitors are present in the aqueous monomer solution at a level of from about 20 to about 2,000 parts per million, and preferably from about 100 to about 1,000 parts per million. The preferred level of polymerization inhibitor will increase as the concentration of the monomer solution increases. Certain of these compounds, such as hydroquinone and hydroquinone monomethyl ether, require the presence of oxygen in order to function as polymerization inhibitors. Thus, it is desirable to ensure that oxygen is present in the aqueous monomer solution when using these polymerization inhibitors. Oxygen can be introduced into the aqueous monomer solution, for example, by bubbling, or sparging, air or oxygen into the aqueous monomer solution. Accordingly, in a preferred embodiment of the present invention the aqueous monomer solution, containing the impurity, is subjected to ultraviolet radiation in the presence of one or more polymerization inhibitors and, optionally, oxygen. The aqueous monomer solution may be exposed to the ultraviolet radiation at a temperature up to the boiling point of the aqueous monomer solution. Preferably, the aqueous monomer solution may be exposed to the ultraviolet radiation at a temperature of from 10°C to 60°C. This temperature range is preferred because it may not require the aqueous monomer solution resulting from the vapor phase oxidation to be heated or cooled. The following Examples are intended to illustrate various embodiments of the present invention. EXAMPLES The following procedure was used to evaluate the effectiveness of ultraviolet radiation at reducing the levels of various carbonyl-containing impurities present in an aqueous solution of acrylic acid. To a 300-milliliter four neck flask equipped with a magnetic stirring bar, an air inlet, a thermometer and an exit and a return tube for the recirculation of monomer, was added 60 grams of 28-32 percent by weight aqueous acrylic acid solution, containing from 400-1,000 parts per million ("ppm") of HQ, prepared by vapor phase oxidation of propylene. The protoanemonin (PTA), furfural and benzaldehyde (PhCHO) levels of the aqueous acrylic acid solution were determined by high pressure liquid chromatography (HPLC) and are reported in ppm based on the aqueous monomer solution. The magnetic stirring bar was activated and air was continuously bubbled through the aqueous monomer solution. A 200 Watt, medium pressure, quartz, mercury vapor lamp (available from Ace Glass Co., Vineland, N.J. catalog no. 7825-32) was turned on, and allowed to equilibrate in a photochemical reactor (available from Ace Glass Co., Vineland, N.J. catalog no. 7878). After fifteen minutes, the aqueous acrylic acid solution was continuously pumped through the exit tube into the photochemical reactor and back to the flask through the return tube. An average residence time of 33 seconds was provided by maintaining a constant volume of 20 milliliters of acrylic acid solution in the photochemical reactor and a flow rate of 36.4 milliliters per minute. The levels of furfural, PTA, PhCHO and HQ were measured periodically by HPLC. The temperature of the aqueous acrylic acid solution remained 24°C. The data appear below. Time (minutes) Furfural (ppm) PTA (ppm) PhCHO (ppm) HQ (ppm) Example 1 0 62 37 43 1016 180 16 25 31 669 Example 2 0 65 39 46 260 180 9 22 28 88 Time (minutes) PTA (ppm) Furfural (ppm) PhCHO (ppm) Example 3 0 50 69 73 30 33 13 63 60 29 8 60 90 24 7 53 120 12 6 44 150 5 6 40 180 4 7 31 Time (minutes) PTA (ppm) Furfural (ppm) PhCHO (ppm) Example 4 0 54 66 74 5 50 58 70 10 45 47 67 20 43 32 61 30 38 19 62 40 37 14 68 50 34 8 63 60 35 7 62 Time (minutes) PTA (ppm) Furfural (ppm) PhCHO (ppm) HQ (ppm) Example 5 0 39 64 44 412 10 35 48 41 -- 20 34 38 41 -- 30 32 29 41 -- 40 31 22 39 -- 50 29 17 35 -- 60 29 16 37 257 The data appearing show the effectiveness of ultraviolet radiation in reducing the level of impurities in aqueous monomer solutions when the aqueous monomer solutions are subjected to ultraviolet radiation.

Claims: A method of reducing the impurity level in an aqueous monomer solution, which comprises subjecting the aqueous monomer solution, containing the impurity, to ultraviolet radiation for from 2 minutes to 5 hours. A method as claimed in claim 1, wherein the aqueous monomer solution is an aqueous solution of acrylic acid, or an aqueous solution of methacrylic acid. A method as claimed in claim 1 or claim 2, wherein the impurity comprises carbonyl-compound impurity. A method as claimed in claim 3, wherein the impurity is selected from acrolein, methacrolein, acetaldehyde, furfural, protoanemonin, formaldehyde, crotonaldehyde, acetone and benzaldehyde. A method as claimed in claim 4, wherein the impurity is selected from furfural, protoanemonin and benzaldehyde. A method as claimed in any preceding claim, wherein the aqueous monomer solution, containing the impurity, is subjected to ultraviolet radiation for from 2 minutes to 5 hours via (a) a single continuous exposure to the ultraviolet radiation, or (b) two or more intermittent exposures to the ultraviolet radiation. A method as claimed in any preceding claim, wherein the aqueous monomer solution, containing the impurity, is subjected to ultraviolet radiation for from 5 minutes to 3 hours. A method as claimed in any preceding claim, wherein the aqueous monomer solution, containing the impurity, is subjected to ultraviolet radiation in the presence of one or more polymerization inhibitors and, optionally, oxygen. A method as claimed in any preceding claim, wherein the aqueous monomer solution is exposed to the ultraviolet radiation at a temperature of from 10°C to 60°C.

Inventors: BAUER WILLIAM JR, QUIROS NELSON IVAN, BAUER, WILLIAM, JR., QUIROS, NELSON IVAN
Applicants: ROHM & HAAS, ROHM AND HAAS COMPANY
Application year: 1994
Main classification: C07C51
IPC codes: C07C51, C07B63, C07C57